Condensation products of the anthraquinone series



UNITE star GEORG KRAENZLEIN AND ERNST DIEFENBACH, OF FBANKFORT-ON-THE-MAIN-HOCHST,

GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., OF YORK, N. Y., A

CORPORATION OF DELAWARE "connnnsn'rron rnonno'rs on THE ANTHRAQUINONE sERIEs "Renewin Application filed-March e, 1931, Serial No. 520,705, and in Germany March 13,1930.

' 'The present invention relates to'new condensation products of the anthraquinone series. f

We have found that new condensation products are obtainable by condensing a co1npound of the following formula:

0 'IITH:

soiox wherein X stands for hydrogen or an alkali metal atom and Y stands for halogen with a compound of the following formula V 'NHz I faoo-mooox wherein R and R represent radicals of the benzene series and X stands for hydrogen or an alkali metal atom, the NH -group in the radical R standing in meta-position and the -COOX-group in the radical R in orthoposition tothe CO-group. The condensation is preferably effected by heating the sodium salts of the components in the presence of water, an acid binding agent, such as sodium carbonate, and a small quantity of a copper compound, such as cuprous chloride or copper sulfate.

The same products are obtainable by con- (lensing a meta-amino-benzoyl-ortho-benzoic acid with a 1-amino-2.i-dihalogen-anthraquinone and exchanging the halogen atom in the l-amino-2-halogen-l-arylido-anthraquim one thus obtained for a sulfonic acid group,

advantageously by treatment with an alkali metal sulfite.

The new products may be characterized by the following formula:

V 5Q wherein the Xs standfor-hydrogen or alkali metal atoms and R and R represents radi- .cals of thebenzene series, the NH-groupin the radical R standing in meta-position and the COOX-group in the radical R in ortho-position to the (JO-group. The new products may be used as acid dyestufis dyeing thefiber blue tints of good fastness to light, washing andfulling, or they may be used as parent materials for the manufacture of other dyestuffs.

- The following examples serve to illustrate the invention but they are not intended-t0 limit it thereto, the parts. being'by weight:

(1) parts of meta-aminobenzoyl5orthobenz'oic acid are dissolved in a solution of 34; parts of anhydrous sodium carbonate in 1000 parts of water. 80 parts of l-amino-4- bromo-anthraquinone 2 sodium sulfonate and 2 parts of cuprous chloride are added thereto. The mixture is, heated to gentleboiling, while vigorously stirring until the formation of the dyestufi' is finished. The dyestufi, obtainable by acidifying with dilute hydrochloric acid or salting out by means of sodium chloride is purified by re-precipitating it from its solution in dilute sodiumcarbonate solution; When dry, the dyestuff forms a blue crystalline powder; it dyes wool beautiful blue tints. V The new dyestufi in the form of its sodium salt, corresponds to the formula:

(2) '51 partslof meta-amino-para-toluylortho-benzoic acid are dissolved in 700 parts 7 of Water and 30 parts of anhydrous sodium 0 carbonate. To this solution there areadded 53 parts of 1-amino-4-bromo-anthraquinone- 2-sodium sulfona-te and 2 parts of cuprous "chloride. The mixture is gently boiledfor 15" hours while well stirring. It is worked up in the usual manner, and the dyestuif is obtained in the form of a blue crystalline powder. It dyes wool blue pure tints of good fastness to light, washing and fulling and 5 corresponds to the formula:

ll I

SOzO.Na

00 d HN I OOONa O NH:

The 3-amino benzophenone-et'.2-dicarbox- ,ylic acid above referred to can be obtained by reducing the corresponding 3'-nitro-benzophenonel.Q-dicarboXylic acid (see Liebigs Annalen der Chemie, vol. 309, page 113) (4) 38 parts of 1-amino-2A-dibromoanthraquinone, 38 parts of meta-amino-paratoluyl-ortho-benzoic acid, 20 parts of anhydrous potassium acetate, 0.5 part of copper acetate and 0.5 part of copper bronze are heated to boiling for 20 hours in 350 parts of amyl alcohol, while stirring. After cooling, the condensation product which has separated, is filtered by suction, washed first with alcohol and then with water and dried.

In order to convert the condensation prodnot into the'sulfonic acid, 10 parts of the crude product thus obtained, 40 parts of phenol, 8 parts of potassium sulfite in 20 parts of water are gently boiled until the dyestufi has become entirely soluble in water. Thephenol is removed by steam distillation from the reaction mixture which is filtered. The dyestuff is precipitated from the filtrate by acidification. It is identical with the dyestuff described in Example 2.

alkali metal atoms, said product forming a alkali metal atoms, said product forming a We claim: 1. As a new product, the compound of the following formula:

so,ox

O NH: ll O HNUOO wherein X and Y stand for hydrogen or blue crystalline powder, dyeing wool beauti- 8O ful blue tints. v

2. As a new product, the compound of the following formula: r r

O NH: :185

sojox wherein X and Y stand for hydrogen or '95 blue crystalline powder dyeing wool ure blue tints of good fastness to light, was ing and fulling.

3. As a new product, the compound of the following formula:

SOIOX ooox "7 4;. As new products, the compounds of the general formula:

O NH: ll

SOnOX wherein the Xs stand for hydrogen or alkali metal atoms and R and R represent radicals of the benzene series, the NH-group in the radical R standing in meta-position and the COOX-group in the radical R in orthoposition to the GO-group, said products forming crystalline powders which dissolve in water to a blue solution and dye wool and silk blue tints of good fastness properties.

In testimony whereof, we aflix our signatures.

GEORG KRAENZLEIN. ERNST DIEFENBAGH. 

